Hydrocarbons in hydrothermal sulfides from the Rainbow Hydrothermal Field

The Rainbow Hydrothermal Field (36°N, Mid-Atlantic Ridge) is one of three presently known fields related to serpentinization of ultramafic rocks accompanied by formation of hydrogen- and methane rich solutions. Gas chromatographic and molecular gas chromatographic - mass spectrometric investigations of sulfide ores and sediments from this field confirmed predominantly biological nature of bitumoids related to high-temperature transformation of biomass of the hydrothermal biological community. At the same time ores of the Rainbow field contain significant amounts of compounds that are not directly related to biogenic synthesis. This fact suggests possibility of abiogenic synthesis of methane and even complex hydrocarbons during serpentinization of ultramafic rocks.

Geochemistry on water profiles from the Kara Sea

As a part of the Russian-German project "Siberian River-Runoff (SIRRO)" the major element composition of the dissolved load and the major and trace element composition of particulate load and bottom sediment of the Yenisei River and Estuary were analyzed and examined in context of the basin lithology and climate. In addition, the processes controlling the transformation of the river load in the estuarine mixing zone were investigated. The chemical composition of the dissolved and particulate load of the Yenisei fluvial endmember is generally comparable to that of other major world rivers. The dissolved load is chiefly controlled by carbonate weathering and the chemical composition of the river suspended particulate matter (SPM) is similar to that of the North American Shale Composite (NASC), which represents the weathering product of the upper continental crust. The Chemical Index of Alteration (CIA) of the Yenisei SPM amounts to 71, which indicates moderate chemical weathering. With regard to the SPM geochemistry, the Yenisei occupies an intermediate position between the adjacent rivers Khatanga and the Lena. Drastic changes in the composition of the river load are seen in the mixing zone between fresh and salt water. While dissolved Na, Ca, Mg, K, CI, S04, F, Br, Sr and HC03 behave conservatively, dissolved Fe is completely removed from solution at very low salinities. Particulate Mn exhibits a pronounced mid-salinity minimum concomitant with a maximum of dissolved Mn, which is probably related to suboxic conditions in the area of the so-called "marginal filter", where highest turbidities are found. The Mn-minimum in SPM is paralleled by depletions of the elements Ba, Zn, Cd, Ni, Cu and V, which can be associated with manganese particles. The estuarine bottom sediments are composed of mud and sand and the sedimentological parameters of the bottom sediments have to be considered for the interpretation of the bulk geochemical data. The chemical composition of the mud is comparable to the SPM, whereas the sand is relatively enriched in Si/Al, Ba/Al, Zr/Al and Sr/Al ratios and depleted in transition metals.

Rare earth elements in standard samples of ocean Fe-Mn nodules and crusts

Contents of rare earth elements (REE) in standard samples of Fe-Mn nodules (SDO-5, 6), Fe-Mn crust (SDO-7), and red clay (SDO-9) have been determined by ICP-MS and instrumental neutron activation analysis. Reproducibility of ICP-MS was 5-6%. These results are discussed and compared with other data. It has been found that distribution of REE in the standard samples of ocean Fe-Mn ores and red clay is highly homogenous.

Geochemistry of tephra from the Taupo Volcanic Zone

The Taupo Volcanic Zone (TVZ), central North Island, New Zealand, is the most frequently active Quaternary rhyolitic system in the world. Silicic tephras recovered from Ocean Drilling Programme Site 1123 (41°47.16'S, 171°29.94'W; 3290 m water depth) in the southwest Pacific Ocean provide a well-dated record of explosive TVZ volcanism since ~1.65 Ma. We present major, minor and trace element data for 70 Quaternary tephra layers from Site 1123 determined by electron probe microanalysis (1314 analyses) and laser ablation inductively coupled plasma mass spectrometry (654 analyses). Trace element data allow for the discrimination of different tephras with similar major element chemistries and the establishment of isochronous tie-lines between three sediment cores (1123A, 1123B and 1123C) recovered from Site 1123. These tephra tie-lines are used to evaluate the stratigraphy and orbitally tuned stable isotope age model of the Site 1123 composite record. Trace element fingerprinting of tephras identifies ~4.5 m and ~7.9 m thick sections of repeated sediments in 1123A (49.0-53.5 mbsf [metres below seafloor]) and 1123C (48.1-56.0 mbsf), respectively. These previously unrecognised repeated sections have resulted in significant errors in the Site 1123 composite stratigraphy and age model for the interval 1.15-1.38 Ma and can explain the poor correspondence between d18O profiles for Site 1123 and Site 849 (equatorial Pacific) during this interval. The revised composite stratigraphy for Site 1123 shows that the 70 tephra layers, when correlated between cores, correspond to ~37-38 individual eruptive events (tephras), 7 of which can be correlated to onshore TVZ deposits. The frequency of large-volume TVZ-derived silicic eruptions, as recorded by the deposition of tephras at Site 1123, has not been uniform through time. Rather it has been typified by short periods (25-50 ka) of intense activity bracketed by longer periods (100-130 ka) of quiescence. The most active period (at least 1 event per 7 ka) occurred between ~1.53 and 1.66 Ma, corresponding to the first ~130 ka of TVZ rhyolitic magmatism. Since 1.2 Ma, ~80% of tephras preserved at Site 1123 and the more proximal Site 1124 were erupted and deposited during glacial periods. This feature may reflect either enhanced atmospheric transport of volcanic ash to these sites (up to 1000 km from source) during glacial conditions or, more speculatively, that these events are triggered by changes in crustal stress accumulation associated with large amplitude sea-level changes. Only 8 of the ~37-38 Site 1123 tephra units (~20%) can be found in all three cores, and 22 tephra units (~60%) are only present in one of the three cores. Whether a tephra is preserved in all three cores does not have any direct relationship to eruptive volume. Instead it is postulated that tephra preservation at Site 1123 is 'patchy' and influenced by the vigorous nature of their deposition to the deep ocean floor as vertical density currents. At this site, at least 5 cores would need to have been drilled within a proximity of 10's to 100's of metres of each other to yield a >99% chance of recovering all the silicic tephras deposited on the ocean surface above it in the past 1.65 Ma.

(Table 1) Redox potential and chemical element contents in CaCO3 and amorphous silica free matter in surface layer bottom sediments of the Pacific Ocean from Hawaiian Islands to Mexico coast

Distribution of Fe, Mn, P, Ti, Cu, Ni, Co, V, Cr, W, Mo, and As in the surface sediment layer on the section from the Hawaiian Islands to the coast of Mexico (Mexico section) is studied. Contents of all studied elements increase from biogenic-terrigenous sediments off the coast of Mexico to pelagic red clays of the Northeast Basin, and more sharply for mobile elements - Mn, Mo, Cu, Ni, Co, and As. In near Hawaii sediments rich in coarsely fragmented volcanic-terrigenous and pyroclastic material of basaltic composition with high contents of Ti, Fe, V, Cr, W, and P, contents of these elements increase sharply, and contents of Mn, Mo, Ni, Co, and Cu for the same reason decrease sharply in comparison with red clay. Abnormally high contents of Mn, Mo, Cu, Ni, Co, and As in the upper layer of hemipelagic and transition sediments of the Mexico section result from diagenetic redistribution and their accumulation on the surface. Processes of diagenetic redistribution in hemipelagic and transition sediment mass of the Mexico section are more rapid than in similar sediments of the Japan section due lower sedimentation rates and higher initial concentrations of Mn. Basic similarity of element distribution regularities in sediments of Japan and Mexico sections is shown.

Geochemistry of bulk sediment from the Cape Basin

A technique for onsite application of X-ray fluorescence (XRF) spectrometry to samples from sediment cores aboard a research vessel was developed and tested. The method is sufficiently simple, precise, and fast to be used routinely for high-resolution analyses of depth profiles as well as surface samples. Analyses were performed with the compact high-performance energy-dispersive polarisation X-ray fluorescence (EDPXRF) analyser Spectro Xepos. Contents of the elements Si, Ti, Al, Fe, Mn, Mg, Ca, K, Sr, Ba, Rb, Cu, Ni, Zn, P, S, Cl and Br were simultaneously determined on 200-225 samples of each core within 24 h of recovery. This study presents a description of the employed shipboard preparation and analysis technique, along with some example data. We show land-based datasets that support our decisions to use powder samples and to reduce the original measuring time for onboard analyses. We demonstrate how well the results from shipboard measurements for the various elements compare with the land-based findings. The onboard geochemical data enabled us to establish an element stratigraphy already during the cruise. Correlation of iron, calcium and silicon enrichment trends with an older reference core provided an age model for the newly retrieved cores. The Spectro Xepos instrument performed without any analytical and technical difficulties which could have been caused by rougher weather conditions or continuous movement and vibration of the research vessel. By now, this XRF technique has been applied during three RV Meteor cruises to approximately 5,000 Late Quaternary sediment samples from altogether 23 gravity cores, 25 multicorer cores and two box cores from the eastern South Atlantic off South Africa/Namibia and the eastern Atlantic off NW Africa.

Geochemistry of ocean floor and forearc serpentinites

We provide new insights into the geochemistry of serpentinites from mid-ocean ridges (Mid-Atlantic Ridge and Hess Deep), passive margins (Iberia Abyssal Plain and Newfoundland) and fore-arcs (Mariana and Guatemala) based on bulk-rock and in situ mineral major and trace element compositional data collected on drill cores from the Deep Sea Drilling Project and Ocean Drilling Program. These data are important for constraining the serpentinite-hosted trace element inventory of subduction zones. Bulk serpentinites show up to several orders of magnitude enrichments in Cl, B, Sr, U, Sb, Pb, Rb, Cs and Li relative to elements of similar compatibility during mantle melting, which correspond to the highest primitive mantle-normalized B/Nb, B/Th, U/Th, Sb/Ce, Sr/Nd and Li/Y among subducted lithologies of the oceanic lithosphere (serpentinites, sediments and altered igneous oceanic crust). Among the elements showing relative enrichment, Cl and B are by far the most abundant with bulk concentrations mostly above 1000 µg/g and 30 µg/g, respectively. All other trace elements showing relative enrichments are generally present in low concentrations (µg/g level), except Sr in carbonate-bearing serpentinites (thousands of µg/g). In situ data indicate that concentrations of Cl, B, Sr, U, Sb, Rb and Cs are, and that of Li can be, increased by serpentinization. These elements are largely hosted in serpentine (lizardite and chrysotile, but not antigorite). Aragonite precipitation leads to significant enrichments in Sr, U and B, whereas calcite is important only as an Sr host. Commonly observed brucite is trace element-poor. The overall enrichment patterns are comparable among serpentinites from mid-ocean ridges, passive margins and fore-arcs, whereas the extents of enrichments are often specific to the geodynamic setting. Variability in relative trace element enrichments within a specific setting (and locality) can be several orders of magnitude. Mid-ocean ridge serpentinites often show pronounced bulk-rock U enrichment in addition to ubiquitous Cl, B and Sr enrichment. They also exhibit positive Eu anomalies on chondrite-normalized rare earth element plots. Passive margin serpentinites tend to have higher overall incompatible trace element contents than mid-ocean ridge and fore-arc serpentinites and show the highest B enrichment among all the studied serpentinites. Fore-arc serpentinites are characterized by low overall trace element contents and show the lowest Cl, but the highest Rb, Cs and Sr enrichments. Based on our data, subducted dehydrating serpentinites are likely to release fluids with high B/Nb, B/Th, U/Th, Sb/Ce and Sr/Nd, rendering them one of the potential sources of some of the characteristic trace element fingerprints of arc magmas (e.g. high B/Nb, high Sr/Nd, high Sb/Ce). However, although serpentinites are a substantial part of global subduction zone chemical cycling, owing to their low overall trace element contents (except for B and Cl) their geochemical imprint on arc magma sources (apart from addition of H2O, B and Cl) can be masked considerably by the trace element signal from subducted crustal components.

Aerosols in the Arctic

In this monograph on the basis of materials obtained by the author and his colleagues in Arctic expeditions of 1991-2005 and of published data results of studies effect of aerosols on environmental conditions and marine sedimentation in the Arctic are summarizes. Processes of aeolian transport and transformation of sedimentary material from sources to places of its accumulation in bottom sediments are described. Results of this study can be used to assess current state of ecosystem of Arctic seas and as a background for evaluation of possible human impact on nature during exploration of mineral resources of the Arctic shelf. For oceanographers, geochemists, geoecologists.

Chemistry of bulk-rocks and minerals of ODP Hole 120-748C

Five hundred meters of a unique Upper Cretaceous Cr-rich glauconitic sequence (Unit III) that overlies a 3-m-thick alkali-basalt flow with underlying epiclastic volcanogenic sediments was drilled at ODP Leg 120 Site 748. The Cr-rich glauconitic sequence is lithostratigraphically and biostratigraphically divided into three subunits (IIIA, IIIB, IIIC) that can also be recognized by the Cr concentration of the bulk sediment, which is low (<200 ppm) in Subunits IIIC and IIIA and high (400-800 ppm) in Subunit IIIB. The Cr enrichment is caused by Cr-spinel, which is the only significant heavy mineral component beside Fe-Ti ores. Other Cr-bearing components are glauconite pellets and possibly some other clay minerals. The glauconitic sequence of Subunit IIIB was formed by reworking of glauconite and volcanogenic components that were transported restricted distances and redeposited downslope by mass-transportation processes. The site of formation was a nearshore, shallow inner shelf environment, and final deposition may have been on the outer part of a narrow shelf, at the slope toward the restricted, probably synsedimentary, faulted Raggatt Basin. The volcanic edifices uncovered on land were tholeiitic basalts (T-MORB), alkali-basaltic (OIB) and (?)silicic volcanic complexes, and ultramafic rocks. The latter were the ultimate source for the Cr-spinel contribution. Terrestrial aqueous solutions carried Fe, K, Cr, Si, and probably Al into the marine environment, where, depending on the redox conditions of microenvironments in the sediment, green (Fe- and K-rich) or brown (Al-rich) glauconite pellets formed. The Upper Cretaceous glauconitic sequence at Site 748 on the Southern Kerguelen Plateau constitutes the transition in space and time from terrestrial to marine, from magmatically active subaerial to magmatically passive submarine conditions, and from a tranquil platform to active rifting conditions.